WO2004092106A2 - Procede de preparation d'alcoxy- et d'aryloxy-phenols - Google Patents

Procede de preparation d'alcoxy- et d'aryloxy-phenols Download PDF

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Publication number
WO2004092106A2
WO2004092106A2 PCT/EP2004/050470 EP2004050470W WO2004092106A2 WO 2004092106 A2 WO2004092106 A2 WO 2004092106A2 EP 2004050470 W EP2004050470 W EP 2004050470W WO 2004092106 A2 WO2004092106 A2 WO 2004092106A2
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WIPO (PCT)
Prior art keywords
formula
acid
reaction
conducted
phenol
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Application number
PCT/EP2004/050470
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English (en)
Other versions
WO2004092106A3 (fr
Inventor
Valerio Borzatta
Oreste Piccolo
Elisa Capparella
Elisa Poluzzi
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Endura S.P.A.
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Publication date
Application filed by Endura S.P.A. filed Critical Endura S.P.A.
Priority to EP04726167A priority Critical patent/EP1638909A2/fr
Publication of WO2004092106A2 publication Critical patent/WO2004092106A2/fr
Publication of WO2004092106A3 publication Critical patent/WO2004092106A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/64—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring

Definitions

  • the present invention relates to a process for preparing alkoxy- and aryloxy- phenols. STATE OF THE ART
  • Alkoxy- and aryloxy-phenols are products which have wide industrial usage.
  • sesamol i.e. 3,4-(methylenedioxy)-phenol is a compound used as an intermediate in the preparation of pharmaceutical products and is also used as an antioxidant, as an antibacterial and herbicidal agent and in the cosmetic industry.
  • Oxidation of aromatic ketones to the corresponding phenols has been used almost exclusively for acetophenones and benzophenones, while the higher homologues of the C 2 -C 6 aliphatic ketones have not been considered because less selective reactions can normally be obtained with the formation of mixtures of esters (cfr. March, Advanced Organic Chemistry, 5 th Edition, Wiley, p. 1417). J. Am. Chem. Soc. 7-1. 14 (1949) describes the oxidation of certain ketones in chloroform with perbenzoic acid with extremely long reaction times (10 days).
  • Synthesis, 1989, 167-171 describes the oxidation of acetophenones to phenols using hydrogen peroxide at high concentration (90%) in the presence of selenium compounds as oxidation catalysts.
  • Synthetic Comm. 29(21 ), 3781-3791 (1999) describes the oxidation of aromatic aldehydes, acetophenones and benzopheno ⁇ es with hydrogen peroxide, activated by boric acid in the presence of sulphuric acid.
  • the present invention comprises a process for the conversion of compounds of formula (I), where X 1( X 2 , n, m and R have the aforestated meaning, which comprises the following stages: a) oxidation of the compound of formula (I) with peracid in an inert organic solvent to give the corresponding ester of formula (II);
  • keto ⁇ e of formula (I) dissolved in an inert solvent is oxidised to the corresponding ester by Baeyer-Villiger oxidation using peracids preformed or generated in situ such as, preferably, performic, peracetic, permaleic, perbenzoic and perphthalic acids.
  • peracids preformed or generated in situ such as, preferably, performic, peracetic, permaleic, perbenzoic and perphthalic acids.
  • the most preferred is performic acid prepared in situ by the reaction of formic acid with hydrogen peroxide.
  • the amount of formic acid can vary from 1.5 to 8 equivalents per mole of ketone, preferably from 2 to 5 equivalents per mole of ketone.
  • the hydrogen peroxide is used from 1 to 6 equivalents per mole of ketone and preferably from 1.2 to 3 equivalents per mole of ketone.
  • the inert solvent is an organic solvent immiscible with water and able to dissolve ketones of formula (I) and carboxylic acid or the corresponding peracid.
  • the inert solvent is chosen from penta ⁇ e, hexa ⁇ e, heptane, octane and their mixtures, dichloromethane, chloroform, carbon tetrachloride and dichloroethane.
  • Chlorinated solvents are preferred. Dichloromethane is particularly preferred.
  • the volume of solvent per mole of the keto ⁇ e of formula (I) used in stage (a) is between 0.05 litres and 1.5 litres preferably between 0.05 litres and 1 litre, more preferably between 0.2 litres and 0.5 litres.
  • the hydrogen peroxide used is that commercially available and easy to handle, with a concentration varying between 30% and 35% (% w/v)
  • the formic acid used has a concentration greater than 80% (% w/w), preferably greater or equal to 85% (w/w).
  • the oxidation reaction is conducted at a temperature between 20° and 80°C, preferably between 30° and 50°C, more preferably between 40° and 50°C.
  • the hydrolysis of the ester of formula (II) can be conducted in a basic or acidic environment.
  • a basic environment is preferred.
  • the base added is an alkaline hydroxide in aqueous solution.
  • Sodium hydroxide is preferred.
  • the base is added in a quantity between 3 and 6 equivalents of sodium hydroxide per mole of ester.
  • the reaction solvent is the same inert solvent used in the reaction of stage (a).
  • reaction mixture derived from stage (a) is used after removing the aqueous phase.
  • the hydrolysis reaction in basic environment is conducted in the presence of a phase transfer catalyst, even more preferably with tetrabutylammonium chloride or Aliquat 360.
  • the phase transfer catalyst is preferably added in a molar ratio between 1/20 and 1/90 per mole of ester of formula (II).
  • a molar ratio between 1/40 and 1/80 per mole of ester is particularly preferred.
  • the acid hydrolysis reaction is conducted in accordance with the known art, in a
  • C1-C1 0 alcoholic solvent preferably in a C 1 -C 3 alcohol, more preferably in methanol.
  • the acid used as catalyst is usually a strong mineral acid, preferably 96% (%w/w) concentrated sulphuric acid.
  • the acid is added in molar ratios between 1% and 2% molar per mole of the ester of formula (II).
  • the acid hydrolysis reaction is conducted at a temperature between 30° and 60°C, more preferably at 40°C.
  • the aqueous phase containing the sodium salt of the phenol of formula (III) is acidified with organic mineral acid, preferably 37% HCI, to release the alkyloxy- or the aryloxy-phenol of formula (III) which is extracted with methylene chloride, D) the methylene chloride is evaporated to obtain a residue which is then distilled and/or crystallised to obtain the alkyloxy- or the aryloxy-phenol.
  • the alkyloxy- or the aryloxy-phenol of formula (III) derived from basic hydrolysis is instead separated from the reaction mixture conducted in stage (b) by a procedure comprising the following operative steps: A') the 2 phases are separated from the reaction mixture; the organic phase containing the unreacted ketone, the non-hydrolysed ester and possibly the catalyst is removed, while the aqueous phase is treated in the same manner as in the aforestated (C) and (D) for the product derived from acid catalysis, but in this case stages (B') and (C) are instead defined thus; B') the aqueous phase containing the sodium salt of the alkyloxy- or aryloxy- phenol of formula (III) is acidified with a strong mineral acid, preferably 37% HCI, to release the corresponding phenolic derivative which is extracted with methylene chloride, C) the methylene chloride is evaporated until a residue is obtained which is then distilled and/or crystallised to obtain the alkyloxy
  • stage (a) Both the unreacted keto ⁇ e derived from hydrolysis under acid catalysis and that obtained under basic catalysis can be easily recycled in stage (a).
  • the reaction mixture is derived from acid hydrolysis the organic phase of stage (a) is recycled, whereas if the hydrolysis is conducted in a basic environment the organic phase of stage (A') is used for the recycling.
  • the organic phase, as well as the ketone and the non-hydrolysed ester also contains the phase transfer catalyst.
  • ketones particularly preferred for use as starting reagents and the corresponding phenols which can be obtained therefrom with the process of the present invention are given below.
  • Ri is ethyl or n-propyl.
  • ketones are prepared in accordance with the known art, or are available commercially.
  • R is ethyl and O-T-0 is CH 2 in the ketone of 5 formula (I), the latter is prepared as described in US 6,342,613.
  • the mixture is then stirred for 10 minutes and the phases are separated.
  • the aqueous phase is extracted with 50 ml of methylene chloride.
  • the organic phase containing the ketone and the non-hydrolysed ester is recycled as described in the
  • the aqueous phase containing the sodium sesamate is then added with 37% HCI till to pH 8.5 to obtain sesamol in free form, which is then extracted with 50 ml of methylene chloride.
  • the organic phase containing the sesamol is concentrated under vacuum at 30°C/23 mbar.
  • the sesamol is distilled at 116°C/3-4 mbar; hydrolysis yield: 94.3%.
  • EXAMPLE 2B Basic hydrolysis of sesamyl propanoate 1325 ml of 4M sodium hydroxide and 3.6 g ( 13 mmoles) of 98% hydrated tetrabutylammo ⁇ ium chloride are added to the organic phase in methylene chloride obtained at the end of the reaction in example 1. After stirring for 8 hours at room temperature, the phases are separated. 200 ml of methylene chloride are added to the aqueous phase, which is added with 37% HCI till to pH 8.5 to release the sesamol which passes into the organic phase. The organic phase is separated and the solvent is evaporated under vacuum at 30°C/23 mbar. The sesamol is distilled at 116°C/23 mbar; hydrolysis yield: 95.8%.
  • EXAMPLE 3A Recycling of the product derived from acid hydrolysis Following hydrolysis in an acid environment as described in example 2A and then treating with aqueous sodium hydroxide in methylene chloride to cause the sesamol to pass into the aqueous phase as sodium sesamate, the ketone and the non-hydrolyzed ester dissolved in the organic phase are reacted as described in example 1.
  • the ketone is added at the same quantity as in example 1 , using the same reaction conditions and the same quantities of reagents given in example 1. Sesamyl propanoate is obtained with an 85% yield with respect to the converted product.
  • EXAMPLE 3B Recycling of the product derived from basic hydrolysis Following hydrolysis in an alkaline environment as described in example 2B, the organic solution containing the unreacted keto ⁇ e and the non-hydrolyzed ester is made up to the same quantity of ketone indicated in example 1 , and reacted as in example 1.
  • the hydrolysis reaction is carried out by the same operative method given in example 3B and using the same molar ratio of sesamyl propa ⁇ oate/NaOH, with no further addition of catalyst. After distillation sesamol is obtained with a hydrolysis yield equal to 94%.
  • EXAMPLE 4 A - Basic hydrolysis 2.32 g ( 8 mmoles) of hydrated tetrabutylammonium chloride are added to the previous organic phase and 664 g (2.7 moles) of 4M NaOH are added over 45 minutes while maintaining the temperature at 20-25°C.
  • the sesamol is distilled at 116°C/3-4 mbar to obtain 82 g of product.
  • the distilled sesamol is crystallised in a 1/2(v/v) mixture of toluene/cyclohexane.
  • the solid obtained is filtered off and dried under vacuum at 40°C/23 mbar. 79 g of crystallised sesamol with a concentration of 99.7% w/w are obtained.
  • the mixture is left under reflux for 6 hours. Then the reaction mixture is cooled, the organic phase is separated and washed with 5 ml of an aqueous solution of 10% sodium sulphite(%w/w) and finally with water. Then 0.12g (0.4mmol) of 98% hydrated tetrabutyl ammonium chloride are added to the organic solution. 32 ml of 4M sodium hydroxide are added at room temperature to the mixture under stirring. The reaction mixture is heated under reflux for six hours and thereafter cooled, until obtaining the separation into two distinct phases. 20 ml of dichloromethane are added to the aqueous phase and afterwards 37% HCI up to a pH value of about 1. The organic phase is washed with water dried on sodium sulphate filtered and evaporated at 30°C/24 mbar.
  • the mixture is heated to the reflux temperature, afterwards it is cooled and the phases are separated.
  • the aqueous phase was treated with 50 ml of dichloromethane and with 37% hydrochloric acid up to a pH value of about 1.
  • the organic phase was washed

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a trait à un procédé de préparation d'alcoxy- et d'aryloxy-phénols, comprenant l'oxydation de la cétone de formule (I) avec des peracides pour obtenir l'ester correspondant de formule (II) qui est ensuite hydrolysé pour obtenir l'aryloxy- ou l'alcoxy-phénol correspondant.
PCT/EP2004/050470 2003-04-18 2004-04-07 Procede de preparation d'alcoxy- et d'aryloxy-phenols WO2004092106A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04726167A EP1638909A2 (fr) 2003-04-18 2004-04-07 Procede de preparation d'alcoxy- et d'aryloxy-phenols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2003A000823 2003-04-18
ITMI20030823 ITMI20030823A1 (it) 2003-04-18 2003-04-18 Processo di preparazione di alcossi e arilossifenoli.

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WO2004092106A2 true WO2004092106A2 (fr) 2004-10-28
WO2004092106A3 WO2004092106A3 (fr) 2004-12-09

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EP (1) EP1638909A2 (fr)
CN (1) CN100467436C (fr)
IT (1) ITMI20030823A1 (fr)
WO (1) WO2004092106A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652833A1 (fr) * 2003-08-07 2006-05-03 Sumitomo Chemical Company, Limited Procede pour produire du 4-hydroxydiphenyl ether

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2289889A1 (fr) 2009-08-18 2011-03-02 Endura S.p.a. Composés phénoxy alkynyl substitués et leurs utilisations
CN102452910B (zh) * 2010-10-20 2014-09-03 昆明制药集团股份有限公司 一种制备3,4,5-三烷氧基苯酚的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999010310A1 (fr) * 1997-08-29 1999-03-04 The Dow Chemical Company Procede de production de diphenylethers et d'esters

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999010310A1 (fr) * 1997-08-29 1999-03-04 The Dow Chemical Company Procede de production de diphenylethers et d'esters

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FRIESS S. L.: "Reactions of Per Acids. I. The Reaction of Perbenzoic Acid with Some Simple Ketones" J. AM. CHEM. SOC., vol. 71, 1949, pages 14-15, XP002296276 cited in the application *
HAWTHORNE M. F. ET AL.: "A Re-examination of the Peroxyacid Cleavage of Ketones. I. Relative Migratory Aptitudes" J. AM. CHEM. SOC., vol. 80, 1958, pages 6393-6398, XP002296180 *
MARTIN H.J. ET AL.: "Synthesis of the C1-C13 Fragment of Kendomycin: Atropisomerism around a C-Aryl Glycosidic Bond" ANGEW. CHEM. INT. ED., vol. 40, no. 17, 2001, pages 3186-3188, XP002296181 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1652833A1 (fr) * 2003-08-07 2006-05-03 Sumitomo Chemical Company, Limited Procede pour produire du 4-hydroxydiphenyl ether
EP1652833A4 (fr) * 2003-08-07 2006-10-11 Sumitomo Chemical Co Procede pour produire du 4-hydroxydiphenyl ether

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Publication number Publication date
CN100467436C (zh) 2009-03-11
CN1777572A (zh) 2006-05-24
WO2004092106A3 (fr) 2004-12-09
ITMI20030823A1 (it) 2004-10-19
EP1638909A2 (fr) 2006-03-29

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